WO2011105878A2 - Adhesive composition - Google Patents

Abstract

The present invention relates to an adhesive composition. According to the present invention, an adhesive having different release forces on either side thereof, and having a modulus of elasticity which varies in a lengthwise direction, can be effectively obtained. By applying the above-described adhesive of the present invention, an optical member, for example a polarizing plate which is thin, effectively prevents light leakage, and has superior durability, can be obtained.

Description

Pressure-sensitive adhesive composition

The present invention relates to a pressure-sensitive adhesive composition, pressure-sensitive adhesive, a pressure-sensitive adhesive manufacturing method, a polarizing plate and a liquid crystal display device.

Liquid crystal displays (LCDs) may include various optical members such as polarizing plates, retardation plates, optical compensation films, reflective sheets, and luminance enhancing films.

For example, the liquid crystal display device may include a liquid crystal panel and a polarizing plate attached to the panel. The polarizing plate may include, for example, a polarizer including an iodine compound or a dichroic dye arranged in a predetermined direction; It may include a protective film attached to both sides of the polarizer, may be formed on the lower portion of the protective film, may include an adhesive layer for attaching the polarizing plate to the liquid crystal panel.

About the polarizing plate of a basic structure, patent document 1 discloses the polarizing plate in which the protective film, the polarizer, the adhesion layer, and the optical film are formed one by one. Patent Document 1 aims to provide a thinner and lighter polarizing plate by removing one of the protective films previously formed on both surfaces of the polarizer.

However, since the polarizer is usually made of a hydrophilic polymer such as polyvinyl alcohol, is vulnerable to moisture or moisture, and also exhibits a property of easily shrinking by performing the stretching process in the manufacturing process, as in Patent Document 1, If the protective film is removed, the performance of the polarizing plate is greatly degraded.

 (Prior art document)

(Patent literature)

  Japanese Patent Publication No. 2002-014226

An object of this invention is to provide an adhesive composition, an adhesive, the manufacturing method of an adhesive, a polarizing plate, and a liquid crystal display device.

The present invention may be referred to as an interpenetrating polymer network (hereinafter referred to as "IPN") containing an acrylic polymer having an alkylene oxide group and an ultraviolet absorber and having the acrylic polymer in a crosslinked state in a cured state. ), And a pressure-sensitive adhesive composition exhibiting different peeling strengths on both surfaces of the sheet shape when cured into a sheet shape.

Hereinafter, the adhesive composition of this invention is demonstrated in detail.

In one example, the pressure-sensitive adhesive composition may be a pressure-sensitive adhesive composition for an optical member such as a polarizing plate, and specifically, may be an pressure-sensitive adhesive composition used to attach the polarizing plate to a liquid crystal panel.

In addition, the sheet shape in the above may be a sheet shape of a single layer, wherein a single layer means a case in which only one layer is present, not two or more layers are stacked.

The pressure-sensitive adhesive composition of the present invention includes an acrylic polymer having an alkylene oxide group, and after curing, includes an IPN structure including a crosslinked structure formed by crosslinking the acrylic polymer and a crosslinked structure of a kind different from the crosslinked structure. do. In one example, the alkylene oxide group may be a straight, branched or cyclic alkylene oxide having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms. Such an alkylene oxide group exhibits a low haze of the pressure-sensitive adhesive layer, and can also effectively suppress light leakage when applied to an optical member such as a polarizing plate or the like. In addition, the alkylene oxide group may be to maintain the peeling force at an appropriate level, even when the elastic modulus of the pressure-sensitive adhesive layer is increased.

The term "IPN structure" refers to a state in which two or more types of crosslinked structures exist simultaneously in the pressure-sensitive adhesive composition after curing, and in the case of the present invention, one of the two or more types of crosslinked structures crosslinks the acrylic polymer. Include. In one example, the two or more types of crosslinked structures may be in an entanglement or in a state of being linked or penetrating with each other. In the above, the acrylic polymer may be included in the IPN structure, for example, in a state crosslinked by a multifunctional crosslinking agent, and such crosslinking may include, for example, blending a multifunctional crosslinking agent capable of crosslinking the polymer in the composition. And, it may be formed by performing an appropriate treatment that can cause the reaction of the crosslinking agent and the polymer in the curing process.

As used herein, the term "curing the adhesive composition" induces a physical action or chemical reaction to the composition by irradiating light, maintaining the adhesive composition at a predetermined temperature, or applying moisture, and thus the adhesive composition. It means the process of expressing the adhesive properties. In the present specification, the cured pressure-sensitive adhesive composition, in some cases, may be used in the same sense as the pressure-sensitive adhesive or pressure-sensitive adhesive layer.

The pressure-sensitive adhesive composition is particularly effective for forming a pressure-sensitive adhesive layer exhibiting different peeling forces on both sides of a sheet after curing in a sheet shape, and the pressure-sensitive adhesive layer is, for example, both sides of the polarizer in the configuration of the polarizing plate. It may be effectively applied when at least one of the protective film formed on the structure to omit the polarizing plate.

In one example, the acrylic polymer may have a weight average molecular weight of 400,000 to 2 million. The weight average molecular weight is a conversion value for standard polystyrene measured by gel permeation chromatography (GPC), and specifically, it is a value measured by the method shown in the following Examples. In the present specification, unless otherwise specified, the term molecular weight means weight average molecular weight. In the present invention, by controlling the molecular weight of the polymer in the above range, it is possible to provide a pressure-sensitive adhesive composition excellent in durability under high temperature or high humidity conditions, and also excellent workability such as coating properties.

In one example, the polymer may include a (meth) acrylic acid ester monomer, a monomer represented by Formula 1 below, and a crosslinkable monomer as a polymer unit.

[Formula 1]

In Formula 1, R represents hydrogen or an alkyl group, A represents alkylene, R ₁ represents an alkyl group or an aryl group, and n represents a number from 1 to 6.

As the (meth) acrylic acid ester monomer, for example, alkyl (meth) acrylate can be used, and alkyl (meth) having an alkyl group having 1 to 14 carbon atoms in consideration of control of cohesion, glass transition temperature and adhesion. Acrylate can be used. Such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) Acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (Meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, tetradecyl (meth) acrylate, and the like can be exemplified, and one or more of the above can be included in the polymer.

The monomer of the said Formula (1) gives an alkylene oxide group to a polymer.

In Formula 1, R may preferably be hydrogen or an alkyl group having 1 to 4 carbon atoms, more preferably hydrogen or a methyl group.

In addition, in Formula 1, A may be a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The groups can have a straight, branched or cyclic structure.

In addition, when R ₁ is an alkyl group in Formula 1, the alkyl group is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. And such alkyl groups may have a straight, branched or cyclic structure.

In addition, in Formula 1, when R ₁ is an aryl group, the aryl group may be an aryl group having 6 to 20 carbon atoms, 6 to 16 carbon atoms, or 6 to 12 carbon atoms.

In addition, n in the general formula (1) may be more preferably 1 to 25, more preferably 1 to 15, more preferably 1 to 6.

 Specific examples of the monomer of Formula 1 include alkoxy alkylene glycol (meth) acrylic acid ester, alkoxy dialkylene glycol (meth) acrylic acid ester, alkoxy trialkylene glycol (meth) acrylic acid ester, alkoxy tetraalkylene glycol (meth) Acrylic ester, alkoxy polyethylene glycol (meth) acrylic acid ester, phenoxy alkylene glycol (meth) acrylic acid ester, phenoxy dialkylene glycol (meth) acrylic acid ester, phenoxy trialkylene glycol (meth) acrylic acid ester, phenoxy tetra Alkylene glycol (meth) acrylic acid ester or phenoxy polyalkylene glycol (meth) acrylic acid ester, etc. are mentioned, One kind or two or more types of these monomers can be contained in a polymer.

As a crosslinkable monomer, a copolymerizable functional group and a crosslinkable functional group may be simultaneously included in a molecule | numerator, and may be copolymerized with the said (meth) acrylic acid ester monomer and the monomer of Formula (1), and may provide the said crosslinkable functional group to a polymer after copolymerization. If so, it can be used without particular limitation.

Examples of the crosslinkable functional group include a nitrogen-containing group such as a hydroxy group, a carboxyl group, an amino group, an isocyanate group, an epoxy group, and the like. Various crosslinkable monomers are known in the art that can provide such crosslinkable functional groups, and these monomers can all be used in the present invention. As a crosslinkable monomer, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth ) Acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate, 2-hydroxypropylene glycol (meth) acrylate, (meth) acrylic acid, 2- (meth) acrylic Loyloxy acetic acid, 3- (meth) acryloyloxy propyl acid, 4- (meth) acryloyloxy butyric acid, acrylic acid duplex, itaconic acid, maleic acid, maleic anhydride, (meth) acrylamide, N -Vinyl pyrrolidone or N-vinyl caprolactam, and the like, but is not limited thereto. It may be included in the polymer which is one kind or two or more kinds of such crosslinkable monomers.

The acrylic polymer, for example, (meth) acrylic acid ester monomer 40 parts by weight to 99.9 parts by weight; 10 parts by weight to 50 parts by weight of the monomer of Formula 1 and 0.01 parts by weight to 30 parts by weight of the crosslinkable monomer. Unless otherwise specified herein, the term "parts by weight" means a weight ratio.

By controlling the weight ratio of the monomer of an acrylic polymer as mentioned above, the adhesive which is excellent in durability, an optical property, etc. can be provided.

The acrylic polymer may further include suitable comonomers in addition to those described above. For example, the acrylic polymer may further include a comonomer represented by the following Chemical Formula 2 in view of controlling glass transition temperature or imparting other functionalities. Can be.

[Formula 2]

In Chemical Formula 2, R ₁ to R ₃ each independently represent hydrogen or alkyl, and R ₄ is cyano; Phenyl unsubstituted or substituted with alkyl; Acetyloxy; Or COR ₅ , wherein R ₅ represents amino or glycidyloxy unsubstituted or substituted with alkyl or alkoxyalkyl.

Alkyl or alkoxy in the definition of R ₁ to R ₅ in Formula 2 means alkyl or alkoxy having 1 to 8 carbon atoms, preferably methyl, ethyl, methoxy, ethoxy, propoxy or butoxy.

Specific examples of the monomer of Formula 2 include nitrogen-containing monomers such as (meth) acrylonitrile, (meth) acrylamide, N-methyl (meth) acrylamide or N-butoxy methyl (meth) acrylamide; Styrene-based monomers such as styrene or methyl styrene; Glycidyl (meth) acrylate; Or a carboxylic acid vinyl ester such as vinyl acetate, or the like, or a heterogeneous compound, but is not limited thereto.

When the acrylic polymer includes the monomer of Chemical Formula 2, the ratio is preferably 20 parts by weight or less.

Such acrylic polymers can be prepared through conventional polymerization methods known in the art. For example, (meth) acrylic acid ester monomers, crosslinkable monomers, and / or monomers of Formula 1, etc., as described above, may be appropriately blended according to the desired weight ratio to prepare a monomer mixture, which is solution polymerization. And photopolymerization, bulk polymerization, suspension polymerization, or emulsion polymerization. If necessary in this process, a suitable polymerization initiator or chain transfer agent may be used together.

The pressure-sensitive adhesive composition may further include a multifunctional crosslinking agent capable of reacting with the acrylic polymer in the curing process to implement a crosslinking structure.

As a polyfunctional crosslinking agent, an appropriate kind can be used in consideration of the crosslinking functional group contained in the said acrylic polymer among well-known crosslinking agents, such as an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent, etc., for example. Examples of the isocyanate crosslinking agent include at least two isocyanate groups such as tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoborone diisocyanate, tetramethylxylene diisocyanate or naphthalene diisocyanate. The crosslinking agent obtained by making a compound or the compound which has two or more isocyanate groups as mentioned above react with a polyol is mentioned, As said polyol, trimethylol propane etc. are mentioned, for example. Moreover, as an epoxy crosslinking agent, ethylene glycol diglycidyl ether, triglycidyl ether, trimethylol propane triglycidyl ether, N, N, N ', N'- tetraglycidyl ethylenediamine and / or glycerin diglycid And dialkyl ethers. Examples of aziridine crosslinking agents include N, N'-toluene-2,4-bis (1-aziridinecarboxamide), N, N'-diphenylmethane-4,4'- Bis (1-aziridinecarboxamide), triethylene melamine, bisisoprotaloyl-1- (2-methylaziridine) and / or tri-1-aziridinylphosphineoxide, and the like, It is not limited. Examples of the metal chelate crosslinking agent include compounds in which polyvalent metals such as aluminum, iron, zinc, tin, titanium, antimony, magnesium or vanadium are coordinated with alkyl esters of acetyl acetone or acetoacetic acid, and the like. However, it is not limited thereto.

The pressure-sensitive adhesive composition or IPN structure may include the crosslinking agent in an amount of 0.01 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the acrylic polymer. Within this range, the cohesion and durability of the pressure-sensitive adhesive can be maintained excellent.

The pressure-sensitive adhesive composition may further include a photopolymerizable compound as a component for implementing a kind of crosslinked structure different from the crosslinked structure in which the acrylic polymer is crosslinked. That is, the IPN structure may further include a crosslinked structure including a polymerized photopolymerizable compound. Such a crosslinked structure may be implemented by blending a photopolymerizable compound in the pressure-sensitive adhesive composition and polymerizing the photopolymerizable compound through irradiation of light in the curing process of the composition. The term "photopolymerizable compound" means a compound containing at least two or more photopolymerizable functional groups in a molecular structure so as to be polymerized by irradiation of light to implement a crosslinked structure. In addition, the photopolymerizable functional group is a functional group that can be polymerized or crosslinked by irradiation with light, and examples thereof include a functional group including an ethylenically unsaturated double bond such as acryloyl group or methacryloyl group, and the like. It doesn't happen. In addition, the term "irradiation of light" means the irradiation of electromagnetic waves, and examples of the electromagnetic waves include microwaves, infrared rays (IR), ultraviolet rays (UV), X rays and γ rays, and α-particle rays ( Particle beams such as α-particle beams, proton beams, neutron beams and electron beams may be included.

As the photopolymerizable compound, for example, multifunctional acrylate (MFA) may be used.

Examples of the polyfunctional acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentylglycol di (meth) acrylate, polyethylene glycol di (meth) acrylic Neopentylglycol adipate di (meth) acrylate, hydroxyl puivalic acid neopentylglycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, Caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate, di (meth) acryloxy ethyl isocyanurate, allylated cyclohexyl di (meth) acrylate , Tricyclodecane dimethanol (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, tricyclodecane Methanol (meth) acrylate, neopentylglycol modified trimethylpropane di (meth) acrylate, adamantane di (meth) acrylate or 9,9-bis [4- (2-acryloyloxyethoxy Difunctional acrylates such as) phenyl] fluorene and the like; Trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide Trifunctional acrylates such as modified trimethylolpropane tri (meth) acrylate, trifunctional urethane (meth) acrylate or tris (meth) acryloxyethyl isocyanurate; Tetrafunctional acrylates such as diglycerin tetra (meth) acrylate or pentaerythritol tetra (meth) acrylate; 5-functional acrylates, such as propionic acid modified dipentaerythritol penta (meth) acrylate; And dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate or urethane (meth) acrylate (ex. Isocyanate monomers and trimethylolpropane tri (meth) acrylate Six-functional acrylates, such as a reactant, etc. can be mentioned, One or a mixture of two or more of these can be used, but it is not limited to these.

In the present invention, it is particularly preferable to use an acrylate having a molecular weight of less than 1,000 and having at least trifunctionality, that is, at least three (meth) acryloyl groups in terms of durability, but is not limited thereto.

Moreover, as a polyfunctional acrylate, it is preferable to use the acrylate containing ring structure and / or urethane bond in molecular structure. In this case, the ring structure included in the acrylate may be a carbocyclic structure or a heterocyclic structure; Or any of a monocyclic or polycyclic structure. Specifically, examples of the ring structure included in the multifunctional acrylate include a cycloalkyl ring structure having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms, such as cyclopentane, cyclohexane, or cycloheptane. One or more ring structures may be included in the acrylate, preferably 1 to 5, more preferably 1 to 3, and one or more hetero atoms such as O, S or N may also be included.

Specific examples of the polyfunctional acrylate including a ring structure and / or a urethane bond as described above include monomers having an isocyanurate structure such as tris (meth) acryloxy ethyl isocyanurate; Reactants of urethane acrylates (ex. Isocyanate compounds having a ring structure in the molecule (ex. Isoborone diisocyanate) and acrylate compounds (ex. Trimethylolpropane tri (meth) acrylate or pentaerythritol tri (meth) acrylate) Etc.), but are not limited thereto.

In the pressure-sensitive adhesive composition or the IPN structure, the photopolymerizable compound is 20 parts by weight to 200 parts by weight, preferably 50 parts by weight to 200 parts by weight, more preferably 60 parts by weight to 150 parts by weight with respect to 100 parts by weight of the acrylic polymer. It can be included in parts by weight, thereby providing an appropriate IPN structure, it is possible to provide a pressure-sensitive adhesive that the elastic modulus and peel force is maintained at the desired level.

The pressure-sensitive adhesive composition includes an ultraviolet absorber, which plays an important role in forming a sheet-shaped pressure-sensitive adhesive having different peeling forces on both surfaces described above.

That is, in order to form the adhesive which has an IPN structure, when the said photopolymerizable compound is included in an adhesive composition, irradiation of light, for example, irradiation of ultraviolet-ray, is necessary for hardening of the said composition. For example, in order to form a sheet-shaped pressure-sensitive adhesive, when the pressure-sensitive adhesive composition is coated to a predetermined thickness and irradiated with ultraviolet rays from one side of the coating layer, the surface of the coating layer to which the ultraviolet rays are irradiated is sufficiently cured to exhibit high elastic modulus, As the ultraviolet light proceeds to the lower part of the coating layer along the thickness direction, the ultraviolet light is absorbed into the coating layer by the ultraviolet absorbent present in the coating layer. Therefore, the amount of ultraviolet rays that reach the lower portion along the thickness direction starting from the surface of the coating layer to which ultraviolet rays are irradiated decreases, and the lowermost coating layer has the least amount of ultraviolet rays, so that the degree of hardening is the least. As a result, in the sheet-like coating layer, a gradient of elastic modulus in which the elastic modulus changes along the thickness direction is formed. In the above, the elastic modulus means tensile modulus or storage modulus. When the elastic modulus is changed along the thickness direction in the sheet-shaped pressure-sensitive adhesive layer as described above, the surface of the coating layer on which the elastic modulus is high, that is, the ultraviolet ray is irradiated at the time of curing, exhibits a low peeling force, but the opposite side has a high peeling force. Can be represented.

As a ultraviolet absorber, if the optical property, elasticity modulus, re-peelability, workability, peeling force, etc. of an adhesive layer are not impaired, it can use without a restriction | limiting in particular.

As a ultraviolet absorber, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'- di-tert- butyl-2'-hydroxyphenyl) benzotriazole, 2 -(5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5- (1,1,3,3, tetramethylbutyl) phenyl) benzotriazole, 2 -(3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-benzotriazole, 2- (3'-tert-butyl-2'-hydroxyphenyl-5'-methylphenyl) -5-benzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl 2- (2'-hydroxyphenyl) -benzotriazole, such as phenyl) -5-benzotriazole or 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole Benzotriazole compounds such as compounds of the class; 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy or 2'-hydroxy- Benzophenone compounds such as 2-hydroxy benzophenone series compounds having 4,4'-dimethoxy functional groups; 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butyl-benzoyl) resorcinol, benzoyl resorcinol, 2,4 -Di-tert-butylphenyl-3,5'-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-4hydroxybenzoate, octadecyl 3, Substituted benzoic acids such as 5-di-tert-butyl-4-hydroxybenzoate or 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate Benzoic acid ester compounds such as compounds having an ester structure; Or a triazine compound may be used, but is not limited thereto.

In the pressure-sensitive adhesive composition, the ultraviolet absorber may be included in an amount of 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of the photopolymerizable compound, but is not limited thereto. The content of the ultraviolet absorbent may be changed in consideration of the curing conditions, the desired elastic modulus or the peel force characteristics of the pressure-sensitive adhesive composition.

The pressure-sensitive adhesive composition may further include a radical initiator to effectively induce a polymerization reaction of the photopolymerizable compound. In one example, the radical initiator may be a photoinitiator, and a specific kind of photoinitiator may be appropriately selected in consideration of curing rate and yellowing potential. For example, a benzoin type, a hydroxy ketone type, an amino ketone type, or a phosphine oxide type photoinitiator etc. can be used, Specifically, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether , Benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylanino acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2 -Hydroxy-2-methyl-1-phenylpropane-1one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1- On, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4 -Dimethylthio Xanthone, 2,4-diethyl thioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylamino benzoic acid ester, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] Propanone], 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. are mentioned. In the present invention, one or more kinds of the above can be used.

The pressure-sensitive adhesive composition may include 0.2 to 20 parts by weight of the photoinitiator based on 100 parts by weight of the photopolymerizable compound. By adjusting the content of the photoinitiator as described above, it is possible to induce an effective curing reaction, to maintain the degree of curing at an appropriate level, and to ensure the storage of the composition.

The pressure-sensitive adhesive composition may further include a silane coupling agent. Such a coupling agent can improve the heat resistance, moisture resistance, etc. of an adhesive. In addition, the coupling agent may act to improve adhesion reliability when the pressure-sensitive adhesive is left for a long time under high temperature or high humidity conditions. Examples of coupling agents that can be used in the present invention include γ-glycidoxypropyl triethoxy silane, γ-glycidoxypropyl trimethoxy silane, γ-glycidoxypropyl methyldiethoxy silane, γ-glycidoxy Propyl triethoxy silane, 3-mercaptopropyl trimethoxy silane, vinyltrimethoxysilane, vinyltriethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxy propyl triethoxy silane, γ-aminopropyl trimethoxy silane, γ-aminopropyl triethoxy silane, 3-isocyanato propyl triethoxy silane, γ-acetoacetatepropyl trimethoxysilane, γ-acetoacetatepropyl triethoxy silane, (beta) -cyanoacetyl trimethoxy silane, (beta) -cyanoacetyl triethoxy silane, and acetoxy aceto trimethoxy silane can be mentioned, A mixture of the above or one or more kinds can be used. In this invention, although it is preferable to use the silane coupling agent which has an acetoacetate group or (beta) -cyanoacetyl group, it is not limited to this. In the pressure-sensitive adhesive composition, the silane coupling agent may be included in an amount of 0.01 to 5 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the acrylic polymer. If the content of the coupling agent is less than 0.01 part by weight, the adhesive increase effect may be insignificant. If it exceeds 5 parts by weight, the durability may be lowered.

The pressure-sensitive adhesive composition may further include a tackifying resin in view of the adjustment of the adhesion performance. The kind of such tackifying resin is not specifically limited, For example, among hydrocarbon type resin, rosin resin, rosin ester resin, terpene resin, terpene phenol resin, polymeric rosin resin, polymeric rosin ester resin, said hydrogenated substance, etc. One kind or a mixture of two or more kinds can be used. The tackifying resin may be included in an amount of 1 part by weight to 100 parts by weight with respect to 100 parts by weight of the acrylic polymer, thereby maintaining excellent compatibility and / or cohesion improvement effect.

The pressure-sensitive adhesive composition further includes at least one additive selected from the group consisting of an epoxy resin, a crosslinking agent, a UV stabilizer, an antioxidant, a colorant, a reinforcing agent, a filler, an antifoaming agent, a surfactant, and a plasticizer within a range that does not affect the effect of the invention. It may further comprise.

The present invention also includes an acrylic polymer having an alkylene oxide group and an ultraviolet absorber, wherein the acrylic polymer is included in the interpenetrating polymer network structure in a crosslinked state and is present on the opposite side of the first surface and the first surface. It is a sheet shape which has a 2nd surface made, and relates to the adhesive which differs in the peeling force in the said 1st surface and a 2nd surface.

The pressure-sensitive adhesive layer can be formed by curing the pressure-sensitive adhesive composition according to the present invention described above, for example. Therefore, individual components, contents, etc. contained in the said adhesive layer are the same as that of the description of the said adhesive composition.

The said adhesive has a sheet form, and peeling force differs on both surfaces of the said sheet form. In the above description, the surfaces of the first surface and the second surface are terms for defining the direction of the adhesive surface in the sheet-shaped adhesive, for example, when one surface is arbitrarily designated as the first surface in the sheet-shaped adhesive. The surface opposite the first surface may be designated as the second surface.

1 is a view showing a cross section of an exemplary pressure-sensitive adhesive 10 of the present invention. As illustrated in FIG. 1, the pressure-sensitive adhesive of the present invention may have a first surface 10A and a second surface 10B when formed in a single layer, and the first and second surfaces 10A and 10B may be different from each other. It is designed to have power.

In the present invention, for example, the first surface may have a lower peel force than the second surface. In addition, the first surface has a peel force against the alkali-free glass is 5 gf / 25mm to 100 gf / 25mm, preferably 5 gf / 25mm to 50 gf / 25mm, more preferably 10 gf / 25mm to 50 gf / It may be 25mm. In addition, the second surface has a peel force against an alkali free glass of 100 gf / 25mm to 1,000 gf / 25mm, preferably 200 gf / 25mm to 800 gf / 25mm, more preferably 200 gf / 25mm to 750 gf It can be / 25mm. Peeling force is the peeling force measured by the method prescribed | regulated in the Example mentioned later in the above. By controlling the peeling force of the first and second surfaces in the above-mentioned ranges, respectively, for example, when the pressure-sensitive adhesive is applied to an optical member such as a polarizing plate, shrinkage and expansion of a functional film such as a polarizer under high temperature or high humidity conditions While suppressing the phenomenon effectively, it is possible to exhibit excellent wettability with respect to an adherend such as a liquid crystal panel.

In order to make the peeling force of both surfaces different from the adhesive of a single layer as mentioned above, the method of manufacturing an adhesive by the method mentioned later using the adhesive composition of this invention mentioned above can be used, for example. That is, in the curing process for producing a sheet-shaped pressure-sensitive adhesive layer, it is possible to form the pressure-sensitive adhesive as described above by forming a gradient in which the elastic modulus changes along the thickness direction of the sheet shape. Referring to FIG. 1, in one example, the pressure-sensitive adhesive layer has a tensile modulus of elasticity along a sheet-shaped thickness direction (arrow T direction in FIG. 1) from the first surface 10A to the second surface direction 10B. A gradient of may be formed. The change in the tensile modulus in the thickness direction in the above means a case where the tensile modulus of the sheet-shaped adhesive increases or decreases continuously or intermittently along the thickness direction. In the present invention, specifically, the tensile modulus may vary along the thickness direction such that the highest tensile modulus appears on the first surface and the lowest tensile modulus appears on the second surface.

When the tensile modulus is controlled to change along the thickness direction as described above, the average tensile modulus of the pressure-sensitive adhesive is 0.1 MPa to 500 MPa, preferably 10 MPa to 400 MPa, more preferably 45 MPa to 300 MPa at 25 ° C. It may be in the range of. By controlling the average value of the tensile modulus in the above range, when the pressure-sensitive adhesive is applied to the optical member, it is possible to effectively suppress the light leakage phenomenon and to exhibit excellent durability at high temperature or high humidity conditions. In addition, the said tensile elasticity modulus is measured by the method described in the Example mentioned later.

In the present invention, the thickness of the pressure-sensitive adhesive is not particularly limited, and may be appropriately selected in consideration of the use of the pressure-sensitive adhesive and the possibility of implementing the pressure-sensitive adhesive in which the elastic modulus changes in the thickness direction.

The present invention also includes an acrylic polymer having an alkylene oxide group and an ultraviolet absorber, and in a cured state, a pressure-sensitive adhesive composition comprising an interpenetrating polymer network structure having the acrylic polymer in a crosslinked state is coated in a sheet form, and Irradiating ultraviolet light from one surface side of a sheet shape to harden the coating layer to prepare a pressure-sensitive adhesive layer, wherein the irradiated ultraviolet light is absorbed in the coating layer while proceeding along the thickness direction of the coating layer, the cured pressure-sensitive adhesive layer It relates to a pressure-sensitive adhesive layer manufacturing method comprising the step of forming a gradient of tensile modulus along the thickness direction of.

That is, in the present invention, the pressure-sensitive adhesive may be prepared by applying the above-described pressure-sensitive adhesive composition or the coating liquid prepared therefrom to a suitable process substrate by conventional means such as a bar coater or a comma coater, and curing.

In this case, the composition includes a ultraviolet absorber, and the ultraviolet rays thus irradiated are absorbed in the course of the thickness direction of the coating layer, thereby forming a gradient of elastic modulus.

FIG. 2 is a diagram schematically illustrating a manufacturing process of one exemplary pressure sensitive adhesive of the present invention, and as shown in FIG. 2, the pressure sensitive adhesive may be formed by irradiating ultraviolet rays to the coating layer 10 of the pressure sensitive adhesive composition. At this time, the irradiation of ultraviolet rays, for example, may form a coating layer 10 of the pressure-sensitive adhesive composition between the two release film 20, it can be carried out on one side of the coating layer (10). At this time, the pressure-sensitive adhesive composition includes an ultraviolet absorber, and the ultraviolet rays irradiated accordingly are absorbed at a predetermined rate in the course of progressing along the thickness direction of the coating layer 10. Accordingly, the surface 10A to which ultraviolet rays are directly irradiated exhibits high elastic modulus and low peeling force due to sufficient curing, whereas the opposite surface 10B exhibits low elastic modulus and high peeling force due to relatively low degree of curing. .

In the present invention, using the pressure-sensitive adhesive composition of the present invention as described above, the type and content of the ultraviolet absorber included in the composition, the thickness of the coating layer (10 in Fig. 2), or the wavelength or intensity of the ultraviolet light to be irradiated, if necessary Etc., the pressure-sensitive adhesive of the desired aspect can be effectively implemented.

On the other hand, the irradiation of the ultraviolet ray, for example, can be carried out using a known means such as a high-pressure mercury lamp, an electrodeless lamp or a xenon lamp (xenon lamp). In addition, ultraviolet irradiation conditions, etc. are not specifically limited, It can select suitably in consideration of the composition of an adhesive composition, and can manufacture effectively the hardened | cured material which changes tensile elasticity modulus in the thickness direction by this. In this case, the illuminance may be about 50 mW / cm ² to 1,000 mW / cm ² , and the light amount may be about 50 mJ / cm ² to 1,000 mJ / cm ² , but is not limited thereto.

In the present invention, in the production method, for the curing efficiency of the pressure-sensitive adhesive composition, the formation of the IPN structure, etc., a process such as heating, drying or aging may be performed in addition to the ultraviolet irradiation process.

The pressure-sensitive adhesive as described above, the gel content represented by the general formula 1 in the state of implementing the IPN structure is preferably 80% by weight or more, more preferably 90% by weight or more.

[Formula 1]

Gel content (% by weight) = B / A × 100

In Formula 1, A represents the mass of the pressure-sensitive adhesive embodying the IPN structure, B represents the dry mass of the insoluble fraction of the pressure-sensitive adhesive obtained after immersing the same pressure-sensitive adhesive in the ethyl acetate at room temperature for 48 hours.

If the gel content is less than 80% by weight, there is a fear that the durability of the pressure-sensitive adhesive is lowered under high temperature and / or high humidity conditions.

In the present invention, the upper limit of the gel content is not particularly limited. For example, the upper limit of the gel content may be appropriately adjusted in the range of 99% or less in consideration of stress relaxation characteristics of the pressure-sensitive adhesive.

The present invention also provides a polarizer; And it relates to a polarizing plate comprising the pressure-sensitive adhesive formed on one surface of the polarizer, in one example, a surface having a relatively low peel force among the first surface and the second surface of the pressure-sensitive adhesive layer is disposed on the polarizer side, relatively The surface having high peeling force may be an adhesive surface for attaching the polarizing plate to the liquid crystal panel.

The kind of polarizer contained in a polarizing plate is not specifically limited. In the present invention, for example, a general polarizer known in the art such as a polyvinyl alcohol polarizer can be used.

The polarizing plate may further include a protective film formed on one side or both sides of the polarizer.

That is, the polarizing plate of the present invention may have a structure in which protective films are formed on both surfaces of the polarizer, for example, and the adhesive according to the present invention is attached to one of the protective films. In some cases, the polarizing plate 3 of the present invention may have a structure in which a protective film is formed only on one surface of the polarizer, and the adhesive according to the present invention is directly formed on the other surface. As such, the structure in which one of the protective films is omitted may be referred to as a thin polarizing plate.

In any case, it is preferable that the surface where the peeling force is relatively low in the pressure-sensitive adhesive is arranged on the polarizer side. As described above, the surface having a low peeling force with respect to the glass is attached to the polarizer, so that even when the protective film is not attached to one surface of the polarizer, the phenomenon in which the polarizer contracts or expands under high temperature or high humidity conditions can be prevented. Moreover, the surface with high peeling force is formed on the opposite side of a polarizer, and can be made to show the outstanding durability, when a polarizing plate is applied to a liquid crystal display device etc.

The kind of protective film which can be included in a polarizing plate in this invention is not specifically limited. In the present invention, for example, cellulose-based film such as triacetyl cellulose; Polyester film such as polycarbonate film or polyethylene terephthalate film; Polyether sulfone-based film; And / or polyolefin films such as polyethylene films, polypropylene films or polyolefin films having a cyclo or norbornene structure or ethylene propylene copolymers; Or a composite film of one kind or more than one kind such as an acrylic film can be used as the protective film. At this time, the thickness of the protective film is also not particularly limited, and may be formed in a conventional thickness.

The polarizing plate of the present invention may further include one or more functional layers such as a waterproof layer, a protective layer, a reflective layer, an antiglare layer, a retardation plate, a wide viewing angle compensation layer, or a brightness enhancement layer. In one example, when the protective film is omitted in the polarizing plate of the present invention, the adhesive layer is attached directly to the polarizer, an adhesive layer may be further formed between the polarizer and the pressure-sensitive adhesive. Examples of the adhesive that can be used in this case include, but are not limited to, an aqueous polyvinyl alcohol adhesive, a solventless acrylic adhesive, or a solventless vinyl acetate adhesive.

In the present invention, the method of manufacturing the polarizing plate by applying the above-described pressure-sensitive adhesive is not particularly limited, and all means known in the art may be employed.

The present invention also relates to a liquid crystal display device comprising a liquid crystal panel and a polarizing plate of the present invention attached to one or both surfaces of the liquid crystal panel.

The kind of liquid crystal panel contained in the liquid crystal display device of this invention as mentioned above is not specifically limited. In the present invention, for example, not limited to the type, F various passive matrix including TN (Twisted Neumatic) type, STN (Super Twisted Neumatic) type, F (ferroelectric) type, PD (polymer dispersed LCD) type, etc. system; Various active matrix schemes including two terminals and three terminals; Both known liquid crystal panels, including IPS mode panels and VA mode panels, can be applied. In addition, the kind and other manufacturing method of the other structure contained in the liquid crystal display device of this invention are not specifically limited, either, The general structure of this field can be employ | adopted and used without limitation.

 In this invention, the adhesive which differs in peeling force in both surfaces and whose elasticity modulus changes along the thickness direction can be provided effectively. In the present invention, by applying the pressure-sensitive adhesive as described above, for example, even when formed to a thin thickness, it is possible to effectively prevent light leakage, it is possible to provide an optical member such as a polarizing plate exhibiting excellent durability.

1 is a cross-sectional view illustrating the pressure-sensitive adhesive of the present invention by way of example.

 2 is a view showing a process of forming the pressure-sensitive adhesive of the present invention by way of example.

Hereinafter, the present invention will be described in more detail with reference to examples according to the present invention and comparative examples not according to the present invention, but the scope of the present invention is not limited to the following examples.

Preparation Example 1 Preparation of Acrylic Polymer

 Nitrogen gas was refluxed, 79 parts by weight of n-butyl acrylate (n-BA), 20 parts by weight of methoxy ethylene glycol acrylate (MEA) and hydroxyethyl acryl in a 1L reactor equipped with a cooling device for easy temperature control. 1.0 parts by weight of HEA was administered. Subsequently, 120 parts by weight of ethyl acetate (EAc) was added as a solvent, and nitrogen gas was purged for 60 minutes to remove oxygen. Then, in the state which kept temperature at 60 degreeC, 0.03 weight part of azobisisobutyronitrile (AIBN) which is a reaction initiator was thrown in, and it was made to react for 8 hours. After the reaction, the mixture was diluted with ethyl acetate (EAc) to prepare an acrylic polymer having a solid content concentration of 15% by weight, a weight average molecular weight of 1.8 million, and a molecular weight distribution of 4.5.

Preparation Examples 2 to 8. Preparation of Acrylic Polymers (B) to (H)

An acrylic polymer was prepared in the same manner as in Preparation Example 1, except that the composition of the monomer was changed as shown in Table 1 below (In Table 1, the acrylic polymer (A) was the same as the polymer prepared in Preparation Example 1). ).

Table 1

Example 1

Preparation of pressure-sensitive adhesive layer

100 parts by weight of the acrylic polymer (A), 3 parts by weight of a polyfunctional crosslinking agent (TDI isocyanate, Coronate L, manufactured by Nippon Polyurethane Co., Ltd.), polyfunctional acrylate (trifunctional urethane acrylate, Aronix M-315, Dongwoo Trading Co., Ltd.) ) 100 parts by weight, 2 parts by weight of hydroxycyclohexylphenyl ketone (Irg 184, manufactured by Ciba Specialty Chemical Co., Ltd.) as a photoinitiator, 2 parts by weight of triazine-based ultraviolet absorber (Tinuvin 400, manufactured by Ciba Specialty Chemical Co., Ltd., Switzerland) A pressure-sensitive adhesive composition was prepared by blending 0.2 parts by weight of a silane coupling agent having a cyanoacetyl group (M812, manufactured by LG Chemical Co., Ltd.) in a solvent such that the solid content concentration was 30% by weight. Thereafter, the prepared pressure-sensitive adhesive composition was coated on a release treated surface of a release treated PET (poly (ethyleneterephthalate)) film (thickness: 38 μm, MRF-38, manufactured by Mitsubishi Corporation) so as to have a thickness of 25 μm, and 110 ° C. Dried in an oven for 3 minutes. Thereafter, a release treatment surface of a release-treated PET film (thickness: 38 μm, MRF-38, manufactured by Mitsubishi Corporation) was further laminated on the dried coating layer to prepare a laminate having the structure shown in FIG. Ultraviolet rays were irradiated using a mercury lamp (roughness: 250 mW / cm ² , light amount: 300 mJ / cm ² ) to form an adhesive layer 10 between two release PET films 20. Hereinafter, for convenience of explanation, the surface of the side to which the ultraviolet-ray is irradiated from the adhesive layer 10 is called 1st surface 10A, and the opposite surface is called 2nd surface 10B.

Preparation of Polarizer

The polyvinyl alcohol-based resin film was stretched, dyed with iodine, and treated with an aqueous boric acid solution to prepare a polarizer. Subsequently, a 60 μm-thick Triacetyl cellulose (TAC) film was attached to one surface of the polarizer with an aqueous polyvinyl alcohol-based adhesive commonly used for attaching a protective film to the polarizer. Subsequently, a polarizing plate was manufactured by laminating the first surface of the prepared pressure-sensitive adhesive layer using the same water-based polyvinyl alcohol-based adhesive as described above on the surface where the TAC film was not attached in the polyvinyl alcohol-based polarizer.

Examples 2-7 and Comparative Examples 1-5

Preparation of Pressure-Sensitive Adhesive Composition

A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that the composition was changed as shown in Tables 2 and 3 below.

TABLE 2

TABLE 3

<Property evaluation>

1. Evaluation of Tensile Modulus

In the present specification, the tensile modulus of the pressure-sensitive adhesive layer is measured by a stress-strain test method by tension in the manner defined in ASTM D638, or when it is difficult to directly measure the tensile modulus, the storage modulus is measured and the following conversion formula It is calculated | required in conversion by. Specifically, the laminate (the laminated structure of the release PET film, the pressure-sensitive adhesive layer, and the release PET film) having the structure shown in FIG. 2 as produced in the Examples or Comparative Examples is 7 cm in length and 1 cm in width. After cutting with dog bone type specimens of size, both ends of the specimens were fixed with a tensile test jig, and the tensile modulus was measured. The measurement conditions of the tensile modulus are as follows.

<Measurement conditions of tensile modulus>

Measuring instrument: Universal Testing Machine (UTM)

Equipment Model: Zwick Roell Z010, Instron

Measuring conditions:

 Load cell: 500 N

 Tensile Speed: 3 mm / sec

<Measurement of storage modulus and conversion to tensile modulus>

The pressure-sensitive adhesive layer is cut to a size of 15 cm × 25 cm × 25 μm (width × length × thickness), and the cut pressure-sensitive adhesive layer is laminated in five layers. Subsequently, the laminated pressure-sensitive adhesive layer was cut into a circle having a diameter of 8 mm, and then left in the compressed state using glass to stand overnight, thereby improving the wetting at the interface between the layers, thereby resulting in bubbles generated during lamination. Prepare the sample by removing. Subsequently, the sample is placed on a parallel plate, the gap is adjusted, the zero point of Normal & Torque is set, the stabilization of the normal force is confirmed, and the following conditions are measured for the storage modulus. The tensile modulus is obtained by

Measuring instruments and measuring conditions

Measuring instrument: ARES-RDA, TA Instruments Inc. with forced convection oven

Measuring conditions:

geometry: 8 mm parallel plate

gap: around 1 mm

test type: dynamic strain frequency sweep

strain = 10.0 [%], temperature: 30 ℃

initial frequency: 0.4 rad / s, final frequency: 100 rad / s

<Conversion type>

E = 3G

In the conversion equation, E represents a tensile modulus, and G represents a storage modulus.

2. Peel force and re-peelability evaluation

Using the pressure-sensitive adhesive layer prepared in Example or Comparative Example, to prepare a polarizing plate in the same manner as in Example 1, to change the direction of the pressure-sensitive adhesive layer in accordance with the surface of the pressure-sensitive adhesive layer to measure the peel force to produce a polarizing plate. . That is, when the peeling force of the first surface is to be measured in the manufacturing process of the polarizing plate presented in Example 1, the second surface is attached to the polarizer side, and when the peeling force of the second surface is to be measured, the first surface is It attaches to the polarizer side and manufactures a polarizing plate. Thereafter, the polarizing plate was cut to a size of 25 mm x 100 mm (width x length) to prepare a specimen. Then, the adhered release PET film on the pressure-sensitive adhesive layer is peeled off, and the surface of the pressure-sensitive adhesive layer is attached to the alkali-free glass using a 2 kg roller in accordance with JIS Z 0237. Subsequently, the alkali-free glass with the pressure-sensitive adhesive layer was pressed for about 20 minutes in an autoclave (50 ° C., 0.5 atm) and stored for 25 hours at constant temperature and humidity conditions (23 ° C., 50% relative humidity). Thereafter, the TA force (Texture Analyzer, manufactured by Stable Micro Systems Co., Ltd.) was used to measure the peeling force while the polarizing plate was peeled off from the alkali free glass at a peel rate of 300 mm / min and a peel angle of 180 degrees. In addition, re-peelability is evaluated based on the following criteria.

<Releasability Evaluation Criteria>

(Circle): When peeling force measured one day after attachment is 800 N / 25 mm or less

(Triangle | delta): When peeling force measured 1 day after attachment is 1,000 N / 25mm or more

X: When the peeling force measured 1 day after attachment is 2,000 N / 25 mm or more

3. Durability Rating

Two specimens were prepared for each of Examples and Comparative Examples, each of which was prepared by cutting the polarizing plates prepared in Examples and Comparative Examples to a size of 90 mm × 170 mm (width × length). Subsequently, the prepared two specimens were attached to both surfaces of the glass substrate (110 mm x 190 mm x 0.7 mm = width x length x thickness) so that the optical absorption axis of each polarizing plate might cross. The pressure applied at the time of attachment was about 5 Kg / cm ² and the operation was performed in a clean room so that bubbles or foreign substances did not occur at the interface. Thereafter, the heat-and-moisture resistance was evaluated by observing whether bubbles or peeling occurred at the adhesive interface after leaving the sample for 1,000 hours at a temperature of 60 ° C. and a relative humidity of 90%. After leaving the sample for 1,000 hours under the temperature condition of 80 ℃, it was evaluated by observing the occurrence of bubbles or peeling at the adhesive interface. The sample prepared immediately before measurement of heat-resistant or heat-resistant durability was left at room temperature for 24 hours, and evaluation was performed. Evaluation conditions are as follows.

Durability Evaluation Criteria

○: no bubbles and peeling

Δ: slight bubbles and / or peeling

×: large amount of bubbles and / or peeling

4. Water resistance evaluation

Samples were prepared by attaching specimens obtained by cutting the polarizing plates prepared in Examples and Comparative Examples to a size of 90 mm × 170 mm (width × length) to one side of a glass substrate (110 mm × 190 mm × 0.7 mm = width × length × thickness). . The pressure applied at the time of attachment was about 5 Kg / cm ^2, and the operation was performed in a clean room so that bubbles or foreign substances did not occur at the interface. Subsequently, the prepared sample was poured into water at a temperature of 60 ° C., left for 24 hours, and then taken out to observe whether bubbles or peeling occurred, and water resistance was evaluated based on the following criteria.

<Water resistance evaluation standard>

○: no bubbles and peeling

Δ: slight bubbles and / or peeling

×: large amount of bubbles and / or peeling

5. Haze Evaluation

Using the adhesive composition of an Example or a comparative example, the sample (adhesive layer thickness: 23 micrometers) of the structure as shown in FIG. 2 was manufactured, and the haze of the adhesive layer in a sample was haze meter (HR-100, Murakamisa, Japan ( Measured) according to JIS K 7105-1 standard.

6. Light transmission uniformity evaluation

The polarizers prepared in Examples and Comparative Examples were attached to both sides of a 22-inch LCD monitor (manufactured by LG Philips LCD) with the optical absorption axes crossed to each other, and were kept for 24 hours under constant temperature and humidity conditions (23 ° C, 50% relative humidity) And then left for 200 hours at a temperature of 80 ° C. Then, the light transmittance was evaluated by the following reference | standard while irradiating light to the said monitor using a backlight in a dark room.

<Light transmission uniformity evaluation criteria>

(Double-circle): When the permeability of light transmittance is not judged visually in the four peripheral parts of a monitor.

(Circle): When the light transmittance nonuniformity is slightly observed by the four peripheral parts of a monitor.

(Triangle | delta): When the light transmittance nonuniformity is observed with the naked eye somewhat in the four peripheral parts of a monitor.

X: When a large amount of light-transmissive nonuniformity is observed by the naked eye in four peripheral parts of a monitor

7. Evaluation of weight average molecular weight and molecular weight distribution

The weight average molecular weight and molecular weight distribution of the acrylic polymer were measured under the following conditions using GPC. The measurement result was converted into the calibration curve using standard polystyrene of Agilent system.

<Weight average molecular weight measurement conditions>

Meter: Agilent GPC (Agilent 1200 series, USA)

Column: Connect 2 PL Mixed B

Column temperature: 40 ℃

Eluent: tetrahydrofuran

Flow rate: 1.0 mL / min

Concentration: ~ 2 mg / mL (100 μL injection)

The measurement results are summarized in Table 4 and Table 5 below.

Table 4

Table 5

As can be seen from the above results, the pressure-sensitive adhesive layers of Examples 1 to 7 exhibited excellent physical properties even when applied to a polarizer in which a protective film was not formed on one surface.

However, when the acrylic polymer forming the IPN structure does not contain the compound of the formula (1) or does not contain the IPN structure, it can be confirmed that at least one or more of the physical properties required for the pressure-sensitive adhesive for the polarizing plate is greatly inferior.

 (Explanation of the sign)

10: adhesive layer

10A: first surface

10B: second surface

20: release PET film

Claims (17)

1. It includes an acrylic polymer having an alkylene oxide group and an ultraviolet absorber, and also includes an interpenetrating polymer network structure having the acrylic polymer in a crosslinked state in the cured state, and different from both sides of the sheet form when cured into a sheet shape. Adhesive composition which shows peeling force.
2.  The pressure-sensitive adhesive composition of claim 1, wherein the acrylic polymer has a weight average molecular weight of 400,000 to 2 million.
3.  The method of claim 1, wherein the acrylic polymer is a (meth) acrylic acid ester monomer; Pressure-sensitive adhesive composition comprising a monomer of the formula (1) and a crosslinkable monomer as a polymerization unit:

    [Formula 1]

   

   In Formula 1, R represents hydrogen or an alkyl group, A represents alkylene, R ₁ represents an alkyl group or an aryl group, and n represents a number from 1 to 50.
4.  4. A monomer according to claim 3, wherein the monomer of formula (1) is an alkoxy alkylene glycol (meth) acrylic acid ester, alkoxy dialkylene glycol (meth) acrylic acid ester, alkoxy trialkylene glycol (meth) acrylic acid ester, alkoxy tetraalkylene glycol (meta ) Acrylic acid ester, alkoxy polyethylene glycol (meth) acrylic acid ester, phenoxy alkylene glycol (meth) acrylic acid ester, phenoxy dialkylene glycol (meth) acrylic acid ester, phenoxy trialkylene glycol (meth) acrylic acid ester, phenoxy The adhesive composition which is tetraalkylene glycol (meth) acrylic acid ester or phenoxy polyalkylene glycol (meth) acrylic acid ester.
5.  The pressure-sensitive adhesive composition of claim 1, wherein the acrylic polymer is included in the interpenetrating polymer network structure in a state crosslinked by a multifunctional crosslinking agent.
6.  The pressure-sensitive adhesive composition of claim 1, wherein the interpenetrating polymer network structure further comprises a crosslinked structure having a polymerized multifunctional acrylate.
7.  The pressure-sensitive adhesive composition of claim 6, wherein the multifunctional acrylate is included in an amount of 20 parts by weight to 200 parts by weight based on 100 parts by weight of the acrylic polymer.
8.  The pressure-sensitive adhesive composition of claim 1, wherein the ultraviolet absorber is a benzotriazole compound, a benzophenone compound, an oxalanilide compound, a benzoic acid ester compound, or a triazine compound.
9.  The pressure-sensitive adhesive composition of claim 1, further comprising a silane coupling agent having an acetoacetate group or a β-cyanoacetyl group.
10.  An acrylic polymer having an alkylene oxide group and an ultraviolet absorbent, wherein the acrylic polymer is also included in the interpenetrating polymer network structure in a crosslinked state, and the second surface is present on the opposite side of the first surface and the first surface. An adhesive is a sheet shape, and the adhesive which differs in peeling force in the said 1st surface and a 2nd surface.
11.  The pressure-sensitive adhesive according to claim 10, wherein the peeling force on the glass of the first surface is 5 gf / 25 mm to 100 gf / 25 mm.
12.  The pressure-sensitive adhesive according to claim 10, wherein the peeling force on the glass of the second surface is 100 gf / 25 mm to 1,000 gf / 25 mm.
13.  The pressure-sensitive adhesive according to claim 10, wherein a gradient of tensile modulus is formed along the thickness direction of the sheet shape from the first surface to the second surface direction.
14.  The pressure sensitive adhesive according to claim 13, which is 0.1 MPa to 500 MPa of average tensile modulus at 25 ° C.
15.  A pressure-sensitive adhesive composition comprising an acrylic polymer having an alkylene oxide group and an ultraviolet absorber and further comprising an interpenetrating polymer network structure having the acrylic polymer in a crosslinked state in a cured state is coated in a sheet form, and one surface of the sheet form The step of curing the coating layer by irradiating the ultraviolet rays from the side, comprising the step of producing a pressure-sensitive adhesive layer, so that the irradiated ultraviolet light is absorbed in the coating layer while proceeding along the thickness direction of the coating layer, the thickness direction of the cured pressure-sensitive adhesive layer Therefore, the method of manufacturing the pressure-sensitive adhesive layer comprising the step of forming a gradient of tensile modulus.
16.  Polarizer; And a pressure-sensitive adhesive layer according to claim 10 formed on one or both surfaces of the polarizer.
17.  A liquid crystal display comprising a liquid crystal panel and a polarizing plate of claim 16 attached to one side or both sides of the liquid crystal panel.

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